Hydrocarbon resins



United States Patent 3,005,806 HYDROCARBON RESINS Morton Fefer, Metuchen, NJ., assignor to Esso Research and Engineering Company, a corporation of Delaware 3,005,806 Patented Oct. 24, 1961 "ice 2 TABLE 1 Steam cracked naphtha fraction boiling between 15 to 130 C.

No Drawing. Filed Oct. 31, 1958, Ser. No. 770,941 6 m G 1 4 Clalms' (CL 260 8z) Component iiiifi e l iflpl r r r g range, weight weight This invention relates to a method for improving the 7 percent percent softening properties of hydrocarbon resins prepared by polymerizing unsaturated hydrocarbo -containing streams 0 r 15 to 50 19 to 30 with a F-riedel-Crafts type catalyst. More particularly 833 33133 it $3222? this invention relates to a methodfor improving the s+ r 100M113) Bio softening point of such a resin without any substantial color degradation by carrying out the polymerization The fractions recited in Table 1 above comprise a mixof the unsaturated hydrocarbon stream in the presence 15 ture of various diolefins, olefins, paraffins and aromatics. of bicycle (2.2.1) hepta-2,5-diene. Table II'shows the various components of the frac- Petroleum resins can be produced from certain untions listed above. i

TABLE 11 Weight percent 1 Olefins Dlolefins Parafifins Aromatics Other hydrocarbons Fraction Specific General Specific General Specific General Specific General Specific General C5f1aCti0H 60 40m 80 1s 10 to 23 10 to o Oto 5 0 Oto 2 C fractionnn 15 4515085 '9, 2to20 s 2to20 0 Oto 10 s Oto 10 C1fracti0n 15 no 25 2o 5m 30 10 std 20 55 30 to 70 0 0to10 Owl-fraction" 0 0to2 0 0to2 0 0 02 use 30to90 40. 20mm 1 Each traction totals 100%. 1 Benzene. 1 Toluene.

saturated petroleum refinery streams which contain vari- As noted from the above table, the wide cut steamous mixtures of acyclic. and cyclic olefins and diolefins rackedfraction comprises substantial amounts of olefinic by contact with a Friedel-Crafts type catalyst under compounds with small amounts of diolefins. This wide relatively low temperatures, e.g., -30 to +90" C. The cut may be used as such or, if desired, a narrow fraction, hydrocarbon mixtures obtained by steam cracking pee.g., C containing steam, which comprises approxitroleum oils have been found to be especially useful for mately 60% olefins and 17% di'olefins may be employed. this purpose. These distillates are prepared by cracking Bicycloheptadiene is substantially absent from even the petroleum fractions such as kerosene, gas oil, naphtha wide boiling fraction since this compound is never formed or residua in the presence of large amounts of steam, in the steam cracking operation. e.g., to 90 mole percent at temperatures of approxi- It is desirable for many uses, e.g., in floor tiles, to obmately =l,000 to l,600,F., This. steam; cracking proc- 50 tain resins having relatively high softening points. The ess is well known in the art and literature. The cracked rior art has suggested the inclusion of various compoliquid fractionboiling largely below C ordinarily connents with the hydrocarbon feed. Also it has been sugtains small amounts of cyclopentadiene monomers, e.g., gested to polymerize a second component in the presence 3 to 5%, which are usually at least partially removed of the finished resin. It has been suggested, for example, by thermal treatment of the fraction to cause dimerizathat divinyl benzene and cyclopentadiene be added to tion of the cyclodiene. The cyclodienes may be left in the resin feed for the purpose of increasing the softening the fraction if it is desired. These resins are useful for point. These additives, while satisfactory for the purthe preparation of floor tiles, in paints, for varnish manposes intended, create problems and have some adverse uf-acture or the like. In general, various steam cracked afiects on the resin. With divinyl benzene additive, the hydrocarbon streams such as described above and more stability, i.e., shelf life, is decreased somewhat, and with particularly below may be employed. For example, a cyclopentadiene there is accompanying the increase in resin may be prepared from feed stocks having a relasoftening point a degradation in color and odor stability. tively wide boiling range, e.g., 15 to 130 C. Typical It has now been found that if a quantity of bicyclo analyses of such a wide boiling steam cracked fraction (2.2.1) hepta-2,5-diene is added to the feed, the resultant are shown in the following table;

resin will have a markedly improved sofitening point with 3,. substantially no accompanying degradation of color and/or odor. The addition of bicycloheptadiene also markedly increases the resin yield. The resins prepared with the above-noted feeds and bicycloheptadiene are more thermally stable than those prepared with the divinyl benzene cross-linking agents and as a result the shelf life for the resin of the present process is considerably longer. The bicycloheptatiene, however, must be added to the steam-cracked feed stock in certain proportions to obtain the desired results: While the concentration of bicycloheptadiene will vary according to the particular steam cracked feed Femployedjini general "it'should be maintained between l'to 35 "wt; percent based on total feed...

It has also been found that =bicycloheptadiene may be added-to the reactionxmixture withoutappreciab le gel formation. With regard to gel formation it is known that oyclopentadienes will under'manyconditions; especially in large batch operations, eifect the formation .of. undesirable gel, whereas the bicyclohept-adiene additives doesnot. have this effect.

The polymerization of steam-crackedpet-roleum hydrocarbons in. thepresence of. bicycloheptadiene-may, be carried. out. in ;any conventional batch, semicontinuous ,or

continuous-fashion, all of which are 'well known :inthe petroleum resin art. The simplest technique-is toadd-the: brcycloheptadiene to the steam-cracked feed prior to its entry into the polymerization reaction vessel. However,

centrations of the bicycloheptadiene additive.

Insofar as the polymerization reaction to produce 357" resins is concerned, the desired hydrocarbon mixture containing the cycloheptadienes is preferably contacted with small amounts of Friedel-Crafts catalyst suchas boron trifiuoride, aluminum chloride, aluminum. bromide or the like. Amounts of from 0.25 to 3.0% onthe unsaturated content of the feed arev preferred. Thecatalyst maybe employed in its solid stateor in solutions, .slurries or complexes. For example, boron trifluoride may..- beuousor batch'operation, there IS preferably employed-in ing in the range of 70 to 125 employed in amounts :from 575%"' the olefin containingfe'edf In carrying out the continuous operation, thereactor is preferably charged with the mixed steam-cracked .petroleum hydrocarbon feed and 'bicycloheptadi'enein the proper proportions. The diluent may be added first, last or at the'same time. The reactor should'comprise means. foriagitating the reaction mixture and the fe'edcontaining the bicycloheptadiene is preferably agitatedduring, the addition :of the catalystand during the entire reaction time. Preferably the catalyst is added slowlyrover a. period *of- 5 minutes to one hour oruntil the desired. catalyst concentration has been-reached.' The-temperature ofthe reactionmixture .may be controlled by any. known technique, a, particularly preferred one is. referred to normally as. a pumpa-round system where the reaction -mixture is continuously circulated through a temperature-controlling bath adapted to either heat or cool the mixture. After the start up of the reaction, the catalyst is continuously added at a rate to give the desired catalyst concentration together with fresh steam-. cracked hydrocarbon feed containing bicycloheptadiene.

The diluent may be by weight based on In a continuous system, a portion of the reaction mixture is continuously drawn olf to a second vessel if'desired to provide additional contact time and the product is withdrawn from the second vessel either batchwise or continuously. One technique for carrying out a batch reaction comprises forming a slurry of the catalyst in diluent and then slowly adding the cracked feed and bicycloheptadiene. The mixture is continuously agitated. If desired, only a portion ofthe aluminum chloride is added initially and the remainder after the reaction is star-ted. The product mixture'is-then quenched, washed and stripped to-give the finalresinproduct- The re action mixture dilute sulfuric or phosphoric acid'to. stop ..the.-reaction. Other quenches such as .the non-ionic. water soluble wetting agents such as the polyethylene oxides, more specifically-such compounds as .alkyl polyethylene.oxide, .alkyl phenyl polyglycols, etc. may, be; employed. all wellknownin the art.v

the-product is water and/or causticiwashed. to' remove any; residual-acidity. Subsequent to. the Washing; theof diluent; unreacted hydrocarboniand .any low molecular weight vpolymer to give Thestripping 'may be carried resinsolu-tion isthen stripped the hard resin product. out in accordance with=well-knowntechniquesby.vacuum or steam distillationv. For example, hard resins-are conveniently recovered by stripping to a bottoms temperature to about 270 C. at 2-5 mm. Hg or the solution may be steam stripped for about 2 hours at 260 C. While the softening point may be raised by increasing the severity and/0r time of stripping, this only results in relatively small increases in softening point and is accompanied by a loss in resin yield with a corresponding increase in undesired liquid polymer.

A single reactor may be employed in lieu of the two reactorsdescribed above; however, in this case the single reactor will preferablycomprise several stages.

For avmore complete understanding of this invention, reference is now hadto the following examples:

EXAMPLE 1 One hundred grams of benzene were added to a reaction flask with 3 grams of, AlCl The mixture was stirred-into aslurryand then 160 grams of a steamcracked naphthafraction boiling in the range of 15 to 50 C. and containing about 17% diolefin, 60% olefin, 1% paraflin and 22% C together with 40 grams of bicycloheptadiene were added. Temperature in the re action mixture was maintained with 3035 C. for a period;.-of.= :about 2 hours with-:agitation;- The reaction product :wasv then withdrawm: quenched with 30 cc. of a .16 wt. percent aqueoussolution-of an alkyl polyether andzwashed with aqueous sodium carbonate 10 percent solution.

molecular weight polymer.

mm; Hg. The; analyses :fOllOWI Resin. 54.5 Raflinate 38.5 Fill 1 7 1 Low molecular weight polymer.

The actual "softening-point of the resin was 99 C.

Thezresin. product in-accelerated resin: agingxtests at.

F. did not show any appreciable degradation over a period of 4,000 hoursrandthe odorof the resin, which:

after being; formed, remained may be'quenched with? an. acid-such as' These are Subsequent to the .-quench,.

The entire reaction mixture was thenstripped .of: diluent, unreacted hydrocarbons and low The product was stripped a column .with..a bottomstemperatureof '270 'C. at'3:

odor rating of 2- III which shows a resin prepared from a steam-cracked petroleum fraction without bicycloheptadiene, and with various concentrations of bicycloheptadiene. The resin feed employed is the same as in Example 1.

TABLE III Run vA B C D Operating conditions blend, g'ms. 200 180 170 160 Blcycloheptadiene added, gms 20 30 40 AlOli,-gms 3 3 3 3 Diluent, gms. (benzene) 100 100 100 100 Temperature, C 30-35 30-35 30-35 30-35 Reaction time, hrs 2 2 2 Products, gms.:

Resin (yield) 77. 3 05 101 106 Ratfinate 196. 5 184 179 172 F111 10. 5 15 l4 l4 Reslnjinspections: Softening point,

0. (actual) 71 86. 5 92 99 It will be noted that aside from the improvement in softening point properties of the resin prepared with bicycloheptadiene, there is an appreciable increase in yield of resin product employing this additive. Thus, in Run A 200 grams of steam-cracked petroleum feed without bi- 1 cycloheptadiene yielded 85 grams of resin, in comparison to a yield of 95-106 grams of product employing 200 grams of combined steam-cracked petroleum fraction and bicycloheptadiene.

What is claimed is:

l. A process for preparing resins which comprises contacting a feed comprising about 65 to 99 wt. percent of an unsaturated C to 0 hydrocarbon fraction boiling within the range of about 15 to 130 C. composed of 10-30 wt. percent of a C fraction having the following composition:

Percent by weight C olefins 40 to 80 C diolefins 10 to 30 C paraflin hydrocarbonsudu..- -10 to 35 C aromatic hydrocarbons 0 to 5 Other C hydrocarbons "a 0 to 2 10-40 wt. percent of a C fraction having the following composition:

C olefins 45 to 85 C diolefins- 2 to 20 C paraffin hydrocarbons 2 to 20 C aromatic hydrocarbons 0 to 10 Other C hydrocarbons 0 to 10 30-55 wt. percent of a C fraction having the following composition:

C olefins 5 to C diolefins 5 to C paraflin hydrocarbons 5 to 20 C aromatic hydrocarbons--- 30 to 70 Other 0-, hydrocarbons 0 to 10 8-25 wt. percent of a C fraction having the following and about 1 to wt. percent of bicycloheptadiene with a Friedel-Crafts catalyst.

2. A process for preparing a petroleum resin which comprises passing to a reaction zone a feed comprising about 65 to '99 wt. percent of an unsaturated C to C steam-cracked petroleum stream boiling within the range of about 15 to 130 C. composed of 10-30 wt. percent of a C fraction having the following composition:

10-40 wt. percent of a C fraction having the following composition: 1

C olefins 45 to 85 C diolefins 2 to 20 C paraflin hydrocarbons 2 to 20 C aromatic hydrocarbons Oto 10 Other C hydrocarbons --a 0 to 10 30-55 wt. percent of a C fraction having the followingcomposition:

C olefins 5 to 25 C diolefins 5 to 30 C paraffin hydrocarbons 5 to 20 C aromatic hydrocarbons 30 to 70 Other C hydrocarbons 0 to 10 8-25 wt. percent of a C fraction having the following composition:

C olefins 0 to 2 0 diolefins 0 to 2 C paraifin hydrocarbons 0 to 2 (3 aromatic hydrocarbons 30 to 90 Other 0 hydrocarbons 20 to 60 and about 1 to 35 wt. percent of bicycloheptadiene, contacting said feed in said reaction zone with a Friedel- Crafts catalyst at a temperature of about -30 to 90 C., and agitating the resulting mixture until a petroleum resin is formed.

3. A process for preparing a petroleum resin which comprises passing to a reaction zone a feed comprising about 65 to 99 wt. percent of a C hydrocarbon fraction containing olefins and diolefins boiling between about 15 and 50 C. composed of 10-30 wt. percent of a C fraction having the following composition:

Percent by weight C olefins 40 to 80 C diolefins 10 to 30 C paraffin hydrocarbons 10 to 35 C aromatic hydrocarbons 0to5 Other C hydrocarbons 0 to 2 10-40 wt. percent of a C fraction having the following composition:

C olefins 45 to C diolefins 2 to 20 C paraffin hydrocarbons--- 2 to 20 C aromatic hydrocarbons 0 to 10 Other C hydrocarbons 0 to 10 30-55 wt. percent of a C fraction having the following composition:

and about 1 to 35 wt. percent of bicycloheptadiene, contacting said feed in said reaction zone Crafts catalyst at a temperature of about 30 to C.

with a Friedeland agitating said resulting mixture until a petroleum resin is formed.

process :for preparing a petroleum resin which comprises passingio a reaction zone'a feed comprising 1 percent of an'unsatur'atedC to (3 about '65 to. 99 wt. hydrocarbon fraction boilingr between"about 15 C. and having the following composition and 130 and "about-1 -to-35 -wt.percent of bic-yclo (2.2.1) -hepta-= 2,5-diene;contating said feed in said reaction-zone withaluminum schloride cata'lyst i at a -temperature "between about -5 and '75 C., agitatinglhe q'esulting rmixturmntil' a Petroleum resin :is' 'formed; withdrawing Ethe' resin-froma said reaction zone; stripping :the lower-flaoiling zimpurities from the reaction 'product and-recoveringia ptroleum resin having good color, goododor and a high softening point.

References Cited in !the file of this patent" UNITED: STATES PATENTS l 2,698,841 McKay Jan; 41195 5 2,750,353 Mil'ViSS et a1. Jllneil2, 1 956'- 2,750,359 Hamn'er et a1. June*12," .19 56- 2,798,865 Banes et ali July:9 1957 

1. A PROCESS FOR PREPARING RESINS WHICH COMPRISES CONTACTING A FEED COMPRISING ABOUT 65 TO 99 WT. PERCENT OF AN UNSATURATED C5 TO C8+ HYDROCARBON FRACTION BOILING WITHIN THE RANGE OF ABOUT 15 TO 130*C. COMPOSED OF 10-30 WT. PERCENT OF A C5 FRACTION HAVING THE FOLLOWING COMPOSITION: 